JPH04257566A - Heterocyclic compound - Google Patents

Abstract

PURPOSE: To provide a heterocyclic compd. useful as a coloring agent for coloring high-polymer org. materials and more particularly plastics by pigments and dyes, and the intermediate thereof.

CONSTITUTION: The compd. of formula I (R¹, R² are alkyl, cycloalkyl, aralkyl, aryl, heterocyclic group; R¹, R⁴ are H, alkyl, aryl, cycloalkyl, aralkyl, heterocyclic group) or the compd. of formula II (X', Y' are O, S, NR⁵, part of 5- or 6-membered heterocycle; R⁵ is H, alkyl, aryl, etc.). The compd. of the formula I is obtd. by bringing the compd. of formula III (R¹² is H, COR⁵) and the compd. of the formula R¹-COCOOR³ into reaction at 30 to 130°C in the presence of a base (e.g.; triethylamine). The compd. of the formula II is obtd. by heating the compd. of the formula I in a melt or a solvent of a high b. p.

COPYRIGHT: (C)1992,JPO

Description

[Detailed description of the invention]

[0001] The present invention provides that one of the tautomers or configurational isomers has the formula

0002

[Chemical formula 3]

[0003] and

0004

[C4]

The present invention relates to a heterocyclic compound corresponding to Here the expression

[0006]

[C5]

Particularly preferred are the compounds ##STR1##.

The substituents in formulas I to III above have the following meanings.

R1 and R2 are optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted aralkyl, optionally substituted aryl, or a double bond having at least one carbon atom, especially a compound of the formula Conjugated with the double bond outside the ring of I or the C=C- double bond of the 5-membered ring of III

0010

Represents a heterocyclic group having an optional substituent containing R3,
R4 and R4 represent hydrogen, alkyl having an optional substituent, aryl having an optional substituent, cycloalkyl having an optional substituent, aralkyl having an optional substituent, or a heterocyclic group having an optional substituent; Y1 represents O, S or NR5, or X1 and Y1 can each form part of a fused 5- or 6-membered heterocyclic ring.

The invention further relates to methods for preparing compounds I-III and methods for their use.

Alkyl preferably represents C1-C18-alkyl, especially C1-C4-alkyl. Cycloalkyl preferably represents C3-C7-cycloalkyl, especially cyclohexyl and cyclopentyl. Examples of suitable substituents for alkyl and cycloalkyl include halogen, such as Cl, Br, F, CN, OCOR10, OR7
, COOR10, SR7, CONR8R9 and OCO
Includes NR8R9. Here, R7 to R10 have the meanings shown below.

Aralkyl stands in particular for phenyl- and naphthyl-C1-C4-alkyl, in which the aryl group can be substituted with the substituents for aryl indicated below.

Aryl preferably represents a carbocyclic aromatic group and may contain 1, 2, 3 and 4, especially 1 or 2, rings such as phenyl, biphenyl and naphthyl.

Suitable heterocyclic groups contain 1, 2, 3 or 4, especially 1 or 2, 5-, 6- or 7-membered rings, at least one of which is composed of O, N and S. (aromatic) heterocycle containing 1, 2 or 3, especially 1 or 2, heteroatoms consisting of: Examples of heterocyclic groups include: pyridyl, pyrimidyl, pyrazinyl, triazinyl, furoyl, pyrrolyl, thiophenyl, quinolyl, coumarinyl, benzofuranyl, benzimidazolyl, benzoxazolyl, dibenzofuranyl, benzothiophenyl. , dibenzothiophenyl, indolyl, carbazolyl, pyrazolyl, imidazolyl, oxazolyl,
isoxazolyl, thiazolyl, indazolyl, benzothiazolyl, pyridazinyl, cinnolyl, quinazolyl,
Quinoxalyl, phthalazinyl, phthalazinedionyl, phthalamidyl, chromonyl, naphtholactamyl, quinolonyl, o-sulfobenzimidyl, maleimidyl, naphthalidinyl, benzimidazolonyl, benzoxazolonyl, benzthioxazolonyl, benzthiazo Thionyl, quinazolonyl, quinoxalonyl, phthalazonyl,
dioxopyrimidinyl, pyridonyl, isoquinolonyl,
Isoquinolinyl, isothioazolyl, benzisoxazolyl, benzisothiazolyl, indazolonyl, acridinyl, acridonyl, quinazolinedionyl, quinoxaledionyl, benzoxazinedionyl, benzoxazinonyl, and naphthalimidyl.

Aryl and heterocyclic radicals include, for example, halogens such as chlorine, bromine and fluorine, -CN, R6,
OR7, SR7, NR8R9, COOR10, COR1
0, NR8COR10, NR8COOR10, NR8C
ONR8R9, NHSO2R10, SO2R10, SO
OR10, CONR8R9, SO2NR8R9, N=N
-R11, OCOR10 and OCONR8R9 can be substituted.

R6 is optionally substituted alkyl, preferably C1-C18-alkyl, especially C1-C4-alkyl, and optionally substituted cycloalkyl, preferably C3-C7-cycloalkyl, especially cyclohexyl and cyclopentyl. be.

Examples of suitable substituents for the alkyl and cycloalkyl radicals R6 include halogen, such as Cl, Br.
,F,CN,OCOR10,OR7,COOR10,S
R7, CONR8R9 and OCONR8R9.

R7, R8 and R9 are hydrogen, optionally substituted alkyl, especially C1-C18-alkyl, preferably C1-C4-alkyl, optionally substituted cycloalkyl, especially cyclohexyl and cyclopentyl, optionally substituted aralkyl, especially phenyl- and naphthyl-C1-C4-alkyl, optionally substituted aryl, especially phenyl and naphthyl, and optionally substituted heterocyclic groups, especially heteroatoms consisting of O, N and S, Represents a 5- or 6-membered heterocyclic group containing 2 or 3 atoms and to which a benzene ring can be fused.

Alkyl and cycloalkyl groups R7, R
8 and R9 are, for example, Cl, Br, F, CN, mono-C
1-C4-alkylamino, di-C1-C4-alkylamino, phenyl or naphthyl can be substituted; these substituents can also be Cl, Br, F, C1-C6-
can be substituted with alkyl and C1-C6-alkoxy groups, and R7, R8 and R9 are O, N
and S, and can be substituted with a 5- or 6-membered heterocyclic group to which a benzene ring can be fused.

Furthermore, R8 and R9 can be taken together to form a 5- or 6-membered ring containing an N atom, such as a morpholino, piperidino or phthalimide ring. Aryl and aralkyl groups R8 and R9 are, for example, C
l, Br, F, C1-C18-alkyl, preferably C
It can be substituted with 1-C4-alkyl, or with C1-C18-alkoxy, preferably with C1-C4-alkoxy.

R10 is hydrogen, optionally substituted alkyl, especially C1-C18-alkyl, preferably C1-C4
-alkyl, optionally substituted cycloalkyl, especially cyclopentyl and cyclohexyl, optionally substituted aralkyl, especially phenyl- and naphthyl-C1-C
4-Alkyl, preferably benzyl, or optionally substituted aryl, especially phenyl and naphthyl.

The radical R10 can carry the same substituents as the corresponding radicals R8 and R9.

R11 is a group of a coupling component, preferably a group of a coupling component of the benzene, naphthalene, acetoacetarylide, pyrazole or pyridone series, or optionally Cl, Br, F, C1-C18-alkyl, preferably C1 ~C4-alkyl, or C1-C18-
represents phenyl substituted with alkoxy, preferably C1-C4-alkoxy.

For the preparation of the components of formula I, the formulas known in the literature or which can be prepared by methods known in the literature are used.

[0026]

[C7]

The compound of formula

[0028]

[Chemical formula 8] R1-COCOOR3
React with compound IV. The radical R12 represents hydrogen or COR5, and R1 to R5 have the same meaning as above.

The reaction is preferably carried out in the presence of a basic catalyst. Aliphatic amines, especially aliphatic tertiary amines, such as triethylamine, are suitable. Preferably, the amines are used in equimolar amounts. The reaction is preferably carried out at a temperature of 30 to 130°C, particularly preferably 50 to 100°C.

The reaction can be carried out without using a solvent. However, it can also be carried out in a solvent. For example, alcohols or dipolar aprotic solvents such as acetonitrile, dimethyl sulfoxide and especially dimethyl formamide are suitable.

In the reaction according to the invention, all four possible configurational isomers Ia, Ib, Ic and Id generally occur.

[0032]

[Chemical formula 9]

Compounds of formula III can be prepared, for example, by heating piperazine derivatives of formula I in a melt or in a high-boiling solvent. Compounds of formula III are also formed by heating compounds of formula I in the presence of a suitable catalyst or dehydrating agent, such as acetic anhydride or phosphorus oxychloride. Examples of suitable solvents are o-dichlorobenzene or high-boiling aromatic hydrocarbons or ethers, and examples of suitable catalysts are p-toluenesulfonic acid or sulfuric acid. The reaction is carried out at a temperature of 100-240°C, especially 120-160°C.
It is preferable to do so. In formula II, the compound of X1 = NR5 is a compound of formula I or
It can be produced by reacting a class amine with a high boiling point solvent in the optional presence of a suitable catalyst, and removing water or a water/alcohol mixture. Compounds of formula III have similar reactivity to aromatic carboxylic anhydrides, such as perylenetetracarboxylic anhydride.

As mentioned above, virtually any primary amine can be used, including highly sterically hindered amines, such as 2,6-diethyl-4-methylaniline, or very weakly basic amines, such as Aromatic amines containing nitro or cyano groups can also be reacted to compounds of formula III. If necessary, an aliphatic amine with a low boiling point can also be reacted in an autoclave.

Compounds of formula VII below, where R5=hydrogen, are prepared by heating compounds of formula I in formamide.

Examples of suitable high-boiling solvents for carrying out the reaction according to the invention are (chlorinated) aromatic hydrocarbons such as xylene, chlorobenzene, dichlorobenzene, trichlorobenzene, naphthalene or chloronaphthalene. Quinoline is particularly suitable. However, water can also be used (especially in autoclaves), or the appropriate amine itself will act as a solvent if it has a sufficiently high boiling point. Advantageously, the water formed in the reaction is removed by azeotropic distillation.

The reaction is preferably carried out at 130-250°C, particularly preferably 180-210°C.

Suitable catalysts are mineral acids, carboxylic acids, sulfonic acids, or metal salts, such as zinc acetate or zinc chloride.

Compounds of formula II with
It is created by sulfiding and changing O atoms to S.

For the preparation of compounds of formula II in which X1 and Y1 form part of a 5- or 6-membered ring with two nitrogen atoms, compound II is combined with a primary aromatic amine, such as 1,
React with 8-diaminonaphthalene or o-phenylenediamine. A typical compound of this type is exemplified by the formula below.

[0041]

[Chemical formula 10]

Preferred compounds of formula II are of the formula

[0043]

[Chemical formula 11]

and especially the formula

[0045]

[Chemical formula 12]

This is a compound corresponding to Here R2, R
4, R5 and X1 have the same meanings as above, and the ring represented by A is, for example, halogen, Cl, Br or F, -NH
COR8 and/or -NR8R9 can be substituted, where R8 and R9 have the meanings given above.

The compounds of formula I are used in particular as intermediates in the preparation of useful dyes and pigments and in particular in the preparation of compounds III.

The compounds of formula III can be used as dyes or as intermediates for the preparation of dyes or pigments, especially II. The compounds of formula III can thus be used as soluble dyes for coloring plastics (polystyrene) or as other disperse dyes, optionally after introducing lipophilic groups.

The compounds of formula II can be used in particular as colorants, which are used, for example, to color high molecular weight organic materials, particularly preferably plastics, with pigments or dyes.

As examples of plastics, mention may be made of homopolymers and copolymers based on polycarbonate, polystyrene, polyacrylate, polymethacrylate, polymethylacrylate and polymethylmethacrylate.

The process of preparing and recovering the compounds of formulas II and III can be controlled so that these compounds are obtained in a form suitable for use as dyes, especially plastics-soluble dyes, or pigments. can.

Examples of suitable thermoplastics in which the colorants of this invention can be used as dyes and pigments include: Cellulose esters such as cellulose nitrate, cellulose acetate, cellulose triacetate, cellulose acetobutyrate or cellulose propionate, cellulose ethers such as methylcellulose, ethylcellulose or benzylcellulose, linear saturated polyester resin plastics, aniline resin plastics, polycarbonate, polystyrene, polyvinyl carbazole,
Polyvinyl chloride, especially hard PVC, polymethacrylate, polyvinylidene chloride, polyacrylonitrile, polyoxymethylene, linear polyurethane, and copolymers, such as vinyl chloride/vinyl acetate copolymers, and especially styrene copolymers, such as styrene. / acrylonitrile copolymer (SAN), styrene/butadiene copolymer (SB
) and styrene/α-methylstyrene copolymer (SM
S).

The above-mentioned high molecular weight compounds can be present individually or in mixtures, as plastic lumps or melts, and can be spun into fibers if desired.

The novel process of the invention is particularly suitable for round dyeing polystyrene, in particular poly(meth)acrylate, preferably polymethyl methacrylate.

The plastics to be colored, preferably in the form of powder, strips or granules, are thoroughly mixed with the dye. This can be achieved, for example, by coating the plastic particles with a finely divided dry dye or by treating the particles with a solution or dispersion of the dye in an organic solvent and then removing the solvent.

In the process according to the invention it is also possible to use mixtures of different dyes of the formula II and/or mixtures of dyes of the formula II with other dyes and/or inorganic or organic pigments.

The process of the invention can also be carried out before or during the polymerization, for example by dissolving the dye in the monomer (mixture) and adding the dye to the monomer (mixture) or prepolymer.

The ratio of dye to plastic can be varied over a wide range depending on the desired color intensity. It is generally advantageous to use a proportion of 0.005 to 30 parts, preferably 0.01 to 3 parts per 100 parts of plastic.

The treated polymer particles can be melted and extruded in an extruder by known methods into products, such as films or fibers, or cast into sheets.

To color plastics with dyes of the formula II, such dyes are, for example, optionally in the form of a masterbatch and mixed with these materials using roll mills, mixers or kneading devices. The pigmented material is then brought into the desired final shape by methods known per se, such as calendering, pressing, extrusion, spreading, casting or injection molding.

In order to produce non-rigid molded articles or to reduce the brittleness of the molded articles, it is often desirable to incorporate plasticizers into the polymer compound before molding. For example, esters of phosphoric acid, phthalic acid or sebacic acid can be used as such. In the process of the invention, plasticizers can be incorporated before or after incorporating the dye.

The compound of formula II can be obtained in a form suitable for pigmentary use or itself by known methods, for example by dissolving or swelling in a strong inorganic acid such as sulfuric acid and by heating on ice. It can be converted into an appropriate form by releasing it into It can also be made into a fine powder by kneading with or without a polishing medium such as an inorganic salt or sand, optionally in the presence of a solvent such as toluene, xylene, dichlorobenzene or N-methylpyrrolidone.

The color strength and transparency of the pigments can be varied by changing the post-treatment method.

Owing to their excellent lightfastness and migration resistance, the compounds of formula II are suitable for a very wide range of applications as pigments. That is, these compounds may be combined with other substances, compositions,
It can be used to mix with coatings, printing inks, colored papers and colored high molecular weight substances to create highly durable pigmented color systems. Mixtures with other substances are understood to mean, for example, mixtures with inorganic white pigments, such as titanium dioxide (rutile) or cement. The compositions are, for example, flash pastes containing organic liquids or pastes or fine pastes containing water, dispersants and optionally preservatives. The term coating material includes, for example, physically or oxidatively drying coatings, heat-curing enamels, reactive coatings, two-component coatings, emulsion paints for weather-resistant coatings, and mud paints.

Printing inks mean inks for printing on paper, textiles and tinplate. Polymeric materials can be naturally occurring, such as rubber, chemically modified, such as cellulose acetate, cellulose butyrate, or viscose, or synthetically produced, such as polymers, addition polymers, and condensation polymers. It can be something. Plastic materials include, for example, polyvinyl chloride, polyvinyl acetate, polyvinyl propionate, polyolefins such as polyethylene, or polymers and copolymers of polyamide, superpolyamide, acrylate, methacrylate, acrylonitrile, acrylamide, butadiene or styrene, and Mention may be made of polyurethanes and polycarbonates. The material pigmented with the compounds of the invention can have any desired shape.

Furthermore, the pigment of formula II has excellent water resistance, oil resistance, acid resistance, lime resistance, alkali resistance, solvent resistance, overcoat resistance, overspray resistance, sublimation resistance, heat resistance, and vulcanization resistance. It has very high tinting power and can be easily distributed in plastic materials.

[0067]

[Example] Example 1 8.2 g of 3-m-chlorobenzylidene-piperazine-
2,5-dione, 4.8 g methylphenylglyoxylate and 3.0 g triethylamine are stirred at 60° C. for 5 hours. The triethylamine is then substantially removed in vacuo and the oily crystalline residue is stirred with 15 ml of methanol for 12 hours. The mixture is then cooled to 0° C. and stirred for a further 2 hours, and the product is filtered off with suction and washed with ice-cold methanol. formula

[0068]

[Chemical formula 13]

8.2 g of the isomer mixture was obtained as a yellowish-white crystalline substance.

Example 2 5 g of the isomer mixture obtained in Example 1 was added to 20 ml of DMF.
Heat at 100°C for 8 hours in a medium. After cooling, the product is filtered with suction and washed with methanol. Green-yellow powder 3.
8g was obtained.

UV (DMF): λmax=384 nm (27,000
)

[0072]

[Chemical formula 14]

When this substance is incorporated into polystyrene, a green-yellow color is produced.

Example 3 7g of 3-p-methoxybenzylidenepiperazine-2,
5-dione, 2 g methylphenylglyoxylate and 3.6 g triethylamine are stirred in 50 ml DMF at 100° C. for 8 hours. The precipitate formed is filtered with suction at room temperature, and 30 ml of methanol is added to the mother liquor. Further product precipitates out as an orange-white crystalline powder. A total of 6.2 g of product was obtained.

UV (DMF): λmax=409 nm (25,300 nm
)

[0076]

[Chemical formula 15]

Example 4 7 g of the isomer mixture obtained in Example 3 was added to 20 ml with 1.3 g of p-methoxyaniline and 0.1 g of zinc acetate.
of quinoline at 190-200°C for 2 hours. The mixture is cooled to 65° C. and then stirred with 30 ml of ethanol and the product is filtered off with suction. formula

0
078]

[Chemical formula 16]

2.8 g of yellow-orange crystalline dye were isolated. This dye gives a yellow color when incorporated into polystyrene.

Example 5 4.0 g of the isomer mixture obtained in Example 2 was mixed with 2 g of p-
12 in 30 ml o-dichlorobenzene with methoxyaniline and 50 mg p-toluenesulfonic acid.
Boil at reflux for an hour. 2.3 g compound after suction filtration at room temperature

[0081]

[Chemical formula 17]

[0082] was separated. This compound appears yellow in polystyrene.

The following compounds in Table 1 were prepared according to the methods of Examples 4 and 5.

[0084]

[Table 1]

[0085]

[Table 2]

[0086]

[Table 3]

[0087]

[Table 4]

[0088]

[Table 5]

[0089]

[Table 6]

[0090]

[Table 7]

Example 42 (Usage example) Formula

[0092]

[Chemical formula 18]

0.1 g of dye 0.1 g, titanium dioxide [Bayertitan (R) R-FK-2]
2 g and 100 g of polystyrene granules are placed in a closed container and mixed on a roller stand for 2 hours. The resulting mixture is extruded at approximately 230° C. into extrudates 2 cm wide, which are granulated again. The granules are injection molded at 230°C using an injection molding machine to form a molded product. A yellow molded product with high heat resistance and good light resistance was obtained.

Example 43 0.02 g of the dye having the formula of Example 42 and 100 g of polystyrene granules are placed in a closed container and mixed for 2 hours on a roller stand. Next, this mixture is injection molded at 230 to 240°C using a screw type injection molding machine to form a molded product. A yellow transparent molded product with high heat resistance and good light resistance was obtained.

Example 44 100 g of commercially available polycarbonate in the form of granules are dry blended with 0.01 g of a dye of the formula described in Example 42. The granules obtained are homogenized in a double screw extruder at 290°C. A transparent yellow color with good lightfastness was obtained. The colored polycarbonate is extruded from an extruder in the form of strands into granules. The granules can be processed and compounded with thermoplastic materials in the usual manner.

Example 45 0.03 g of the dyestuff of the formula described in Example 42 is dissolved in 99.97 g of methyl methacrylate. After adding 0.1 g of dibenzoyl peroxide, the solution is heated to 120° C. to initiate polymerization. After 30 minutes, the partially polymerized methyl methacrylate is completely polymerized at 80° C. between two glass plates for 10 hours. A yellow transparent sheet of polymethyl methacrylate was obtained.

The main features and aspects of the present invention are as follows. 1. One of the tautomers or configurational isomers has the formula

0098
]

[Chemical formula 19]

In the formula, R1 and R2 are optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted aralkyl, optionally substituted aryl, or a double ring outside the ring of formula I. Represents a heterocyclic group optionally having a substituent containing a double bond having at least one carbon atom conjugated with a bond, R3 and R4 are hydrogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted. A compound corresponding to a substituted cycloalkyl group, an optionally substituted aralkyl group, or an optionally substituted heterocyclic group.

[0100]2. One of the tautomers or configurational isomers has the formula

[0101]

[C20]

In the formula, R1 and R2 are optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted aralkyl, optionally substituted aryl, or C=C- in the 5-membered ring of formula II. Represents a heterocyclic group having an optional substituent containing a double bond having at least one carbon atom conjugated with a double bond, R4 has the meaning described in item 1 above, X1 and Y1 are O, S or NR5 or X1 and Y1 can each form part of a fused 5- or 6-membered heterocyclic ring, R5 being hydrogen, optionally substituted alkyl, optionally substituted Compounds corresponding to aryl, optionally substituted cycloalkyl, optionally substituted aralkyl, or optionally substituted heterocyclic group.

3. formula

[0104]

[C21]

The compound according to item 2 above, having the formula:

4. formula

[0107]

[C22]

The compound according to item 2 above, wherein X1 represents NR5.

5. formula

[0110]

[C23]

[0111] The compound according to item 2 above, wherein the ring represented by A in the formula can have a substituent.

6. A method of coloring a high molecular weight organic material with a dye or pigment using the compound described in item 2 above.

7. A method for coloring a homopolymer or copolymer based on polycarbonate, polystyrene, polyacrylate, polymethacrylate, polymethyl acrylate or polymethyl methacrylate with a dye or pigment using a compound according to item 2 above.

8. A coloring method using the compound described in item 2 above.

9. A method for producing the compound described in item 2 above, using the compound described in item 1 above as an intermediate.

10. A method for producing the compound described in item 2 above, using the compound described in item 3 above as an intermediate.

Claims (2)

[Claims] Claim 1: One of the tautomers or configurational isomers has the formula: [Image Omitted] In the formula, R1 and R2 are optionally substituted alkyl,
optionally substituted cycloalkyl, optionally substituted aralkyl, optionally substituted aryl, or at least one carbon atom conjugated to a double bond external to the ring of formula I
R3 and R4 are hydrogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted cycloalkyl, optionally substituted A compound characterized in that it corresponds to an aralkyl group having a group or a heterocyclic group having an optional substituent group. Claim 2: One of the tautomers or configurational isomers has the formula: [Claim 2] In the formula, R1 and R2 are optionally substituted alkyl,
optionally substituted cycloalkyl, optionally substituted aralkyl, optionally substituted aryl, or a double bond having at least one carbon atom conjugated with the C═C double bond of the five-membered ring of formula I; represents a heterocyclic group having optional substituents, R4 is hydrogen, alkyl optionally having substituents,
represents an optionally substituted aryl, optionally substituted cycloalkyl, optionally substituted aralkyl, or optionally substituted heterocyclic group, X1 and Y1 represent O, S or NR5, or X1 and Y1 can each form part of a fused 5- or 6-membered heterocyclic ring, R5 is hydrogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted cycloalkyl , an optionally substituted aralkyl group, or an optionally substituted heterocyclic group.